Computational insights into radical hydrogenation of alkenes and naphthalenes with Ar3P–OH radical

Abstract

The Ar₃P–OH radical-mediated hydrogenation proceeds through a concerted proton-coupled electron transfer (cPCET) pathway rather than a hydrogen atom transfer (HAT) mechanism. A binary linear model incorporating LUMO coefficients and charge populations has been developed to rationalize the regioselectivity of radical hydrogenation of naphthalene derivatives.